Anion recognition through noncovalent interactions stands as an emerging field in supramolecular chemistry, exerting a profound influence on the regulation of biological functions. Herein, the thermodynamics of complexation between sodium cyanate (NaOCN) and calix[4]pyrrole was systematically investigated by linear and nonlinear IR spectroscopy, highlighting enthalpy changes as the dominant driving force. The overall orientational relaxation of bound anion can be described by an Arrhenius-type activated process, yielding an activation energy of 15.0 ± 1.0 kJ mol-1. The structural dynamics of contact ion pairs (CIPs) formed between Na+ and OCN- in solution showed a negligible temperature effect, suggesting entropy changes as the principal governing factor. Further analysis revealed that anion recognition in solution is mediated by conformational changes of the receptor and collective rearrangement of hydrogen bond dynamics. This study, framed within the paradigms of thermodynamics and ultrafast structural dynamics, substantially advances our comprehension of the microscopic mechanisms underlying anion recognition in the realm of supramolecular chemistry.